Saturated indane derivatives and processes for producing same

ABSTRACT

SATURATED INDANE DERIVATIVES HAVING THE FORMULA   1,1,2,3,3-PENTA(CH3-),(R-O-)PERHYDROINDANE   WHEREIN R IS HYDROGEN, ALKYL OF 1 TO 5 CARBON ATOMS, OR ALKYLACYL OF 1 TO 5 CARBON ATOMS; AND PROCESSES FOR PRODUCING SAME.

United States Patent US. Cl. 260-617 F 3 Claims ABSTRACT OF THEDISCLOSURE Saturated indane derivatives having the formula wherein R ishydrogen, alkyl of 1 to 5 carbon atoms, or al'kylacyl of 1 to 5 carbonatoms; and processes for producing same.

This application is a division of US. application Ser. No. 851,048 filedon Aug. 18, 1969, now US. Pat. 3,681,464.

BACKGROUND OF THE INVENTION There is a continuing need for fragrancematerials having desirable woody amber odors with satisfactory olfactoryovertones or qualities. Many natural products have such woody amberfragrances, but the more desirable of these are frequently in shortsupply, and hence difiicult to obtain and expensive. Further, while bothnatural and some synthetic materials can provide woody amber fragrancequalities, many of these are fleeting and unsuitable for use in qualityperfumes or other olfactory compositions. Moreover, it is desirable tohave such fragrance materials with musk, fruit-like, or similarovertones which can be blended with other materials.

THE INVENTION Briefly, the present invention provides novel saturatedindane derivatives having the formula wherein R is a carbonyl oxygen ora hydroxy, acyloxy, or alkyloxy group. These substances have apersistent strong woody amber fragrance with fruit-like and musk aromanotes. Thus, the present invention also provides novel perfume andfragrance compositions containing such indane derivatives, and processesfor producing such derivatives are also disclosed herein.

More specifically, the indanones contemplated herein are1,1,2,3,3-pentamethylhexahydro-4(5)-indanone having the formula3,767,713 Patented Oct. 23, 1973 and 1,1,2,3,3-pentamethylhexahydro-5(4H)-indanone having the formula The indanols and derivativescontemplated according to this disclosure include1,1,2,3,3-pentamethylhexahydroindan-4-ol having the formula 1,1,2,3,3pentamethylhexahydroindan 5 01 having the formula the correspondingindanyl alkyl ethers according to the formulas and and

In the foregoing formulas R is a lower alkyl group, desirably one havingfrom one to five carbon atoms, with methyl being a preferred lower alkylgroup; and R is a lower alkyl acyl group having from one to five carbonatoms, with the acetyl group. being preferred. It will be appreciatedfrom the present disclosure that the foregoing materials can exist inseveral stereoisomeric forms, and it is contemplated that the formulasgiven above include the several isomeric forms.

The alcohols can be prepared directly from the correspondingpentamethylindane by sulfonation, alkali fusion, and hydrolysis toprovide pentamethylindanol and then hydrogenation to thehexahydropentamethylindanol. Alternatively, the saturated3a,7a-epoxypentamethylindane can be treated with an aluminum trialkoxideto form the monounsaturated alcohol.

The alcohols can also be produced directly from pentamethylindane bytreatment with an acyl halide such as acetyl chloride or the like in thepresence of a Friedel- Crafts catalyst followed by oxidation of theindanealkyl ketone with a peroxygen material such as peracetic acid andthe like to provide the indanyl ester. Hydrolysis of the ester providesthe indanol which is then hydrogenated as set forth below to afford thesaturated indanol. A tetrahydroindanol can also be obtained by Birchreduction of S-indanol as shown in J. Am. Chem. Soc., 89, 1044. Thetetrahydroindanols so prepared are then hydrogenated and oxidized to theketone, as taught hereinafter.

The ketones of this invention can be produced by a number of routes. Onepreferred route is the oxidation of a saturated or unsaturated 4-indanolor S-indanol under conditions providing the corresponding ketone.According to this preferred route, any reagent which will convert asecondary hydroxyl to a carbonyl oxygen can be used. Exemplary of suchoxidizing agents are I ones reagent (a chromium trioxide-sulfuric acidmixture) and oxygen-metal systems.

The oxidation of the hydroxyl group is carried out on a hydrogenatedindanol. In the event that the ketone is not saturated the six-mcmberedring is subsequently hydrogenated with a catalyst under conditions whichwill not reduce the carbonyl group. Suitable catalysts for this reactioninclude metallic catalysts such as Raney nickel, or noble metals such asplatinum, palladium, and the like utilized at substantiallysuperatmospheric pressures on the order of 50 to 125 atmospheres. It ispreferred to carry out the hydrogenation at from 1000 to about 1500p.s.i.g. at 150 to 250 C.

The oxidation is carried out by treating the secondary alcohol withhexavalent chromium or oxygen-metallic catalyst oxidizing systems. It isdesirable in carrying out such a reaction that the alcohol be dissolvedor dispersed in a reaction vehicle which serves to moderate the reaction and provide better control. Suitable vehicles include oxygenatedsolvents such as acetone or lower carboxylic acids such as acetic acid.It will be understood that mutual solubility of the indanyl alcohol andoxidizing agent in the reaction vehicle is preferred.

The Jones reagent is prepared by dissolving chromium trioxide or alkalimetal dichromate in aqueous sulfuric acid, e.g., 30% to 50% H 50preferably 40% H 50 At least an equimolar quantity of the oxidizingagent is i mixed with the indanol in the reaction vehicle for bestresults. It is preferred to use an excess of oxidizing agent up to about50 molar percent based upon the weight of the indanol, and a molarexcess of 25 to 40% is preferred. The oxidation is carried out at mildtemperatures on the order of -30 C. In a preferred embodiment of theinvention, the reaction is carried out at -20" C.

The oxidation to provide the ketones can also be carried out with theoxygen-metallic catalyst system disclosed above. In this case the oxygencan either be pure or in admixture with an inert diluent such asnitrogen or the like. The catalyst is preferably a metal such as silver.Copper can also be used.

After the reaction to produce the ketone is completed, the product canbe separated from the vehicle and any unreacted materials or unwantedby-products removed by conventional means including washing,distillation, crystallization, extraction, preparative chromatography,and the like. It is preferred to fractionally distill the Washedreaction product under relatively high vacuum so as to obtain a pureproduct. Product purities of 80% are readily obtained, and much higherpurities can also be provided by suitable treatment. All parts,proportions, percentages and ratios herein are by weight unless otherwise indicated.

The pentamethylhexahydroindanones of this invention are useful asfragrances. They can be used singly or in combination to contribute awoody amber fragrance. As olfactory agents the indanones of thisinvention can be formulated into or used as components of a perfumecomposition.

The term perfume composition" is used herein to mean a mixture oforganic compounds, including, for example, alcohols, aldehydes, ketones,esters and frequently hydrocarbons which are admixed so that thecombined odors of the individual components produce a pleasant ordesired fragrance. Such perfume compositions usually contain: (a) themain note or the bouquet or foundation-stone of the composition; (b)modifiers which round-off and accompany the main note; (c) fixativeswhich include odorous substances which lend a particular note to theperfume throughout all stages of evaporation, and substances whichretard evaporation; and (d) topnotes which are usually low-boilingfresh-smelling materials.

In perfume compositions the individual component will contribute itsparticular olfactory characteristics, but the overall effect of theerfume composition will be the sum of the effect of each ingredient.Thus, the individual compounds of this invention, or mixtures thereofcan be used to alter the aroma characteristics of a perfume composition,for example, by highlighting or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of the compounds of this invention which will be effective inperfume compositions depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 2% byWeight of mixtures or compounds of this invention, or even less, may beused to impart a woody amber odor to soaps, cosmetics, and otherproducts. The amount employed can range up to 7% or higher and willdepend on considerations of cost, nature of the end product, the effectdesired on the finished product and the particular fragrance sought.

The indanones of this invention can be used alone or in a perfumecomposition as olfactory components in detergents and soaps; spacedeodorants; perfumes; colognes; bath preparations such as bath oil andbath salts; hair preparations such as lacquers, brilliantines, pomadesand shampoos; cosmetic preparations such as creams, deodorants, handlotions and sun screens; powders such as tales, dusting powders, facepowder, and the like. When used as an olfactory component of a perfumedarticle, as little as 0.01% of the novel ketones will suffice to imparta woody amber odor.

In addition, the perfume composition can contain a vehicle or carrierfor the other ingredients. The vehicle can be a liquid such as alcohol,glycol, or the like. The carrier can be an absorbent solid such as a gumor components for encapsulating the composition.

It will also be appreciated that the pentamethylhexahydroindanonesaccording to this invention can be used to enhance, modify, orsupplement the fragrance properties of natural or synthetic fragrancecompositions. Thus, the indanones can be used in fragrance compositionsfor addition to perfume compositions or directly to products such assoap, detergents, cosmetics, and the like. The fragrance compositions soprepared do not entirely provide the olfactory properties to thefinished perfume or other article, but they do furnish a substantialpart of the overall fragrance impression.

The following examples are given to illustrate embodiments of theinvention as it is presently preferred to practice it. It will beunderstood that these examples are illustrative, and the invention isnot to be considered as restricted thereto except as indicated in theappended claims.

EXAMPLE I (a) Preparation of pentamethylindanesulfonic acid A five-literflask equipped with a stirrer, condenser, and dropping funnel is chargedwith 1500 g. of concentrated sulfuric acid, and 400 g. of1,1,2,3,3-pentamethylindane is added dropwise while the temperature ismaintained at 3035 C. After addition is completed stirring is continuedfor an additional hour.

A five-liter flask is set up with a thermometer and immersed in a DryIce-isopropanol bath, and one liter of water is charged to the flask.After the water is cooled to C. the foregoing reaction mixture is addeddropwise to the water while the 10 temperature is maintained. Theaddition of reaction mixture to the water is completed and he stirringis continued for 30 minutes before filtering the flask contents througha Buchner funnel under vacuum. The solids so obtained are pressed toremove water.

The solids are rinsed in 100 ml. of 1% hydrochloric acid at 0 C. andpressed to obtain 822.2 g. of crude crystals. After overnight drying ina vacuum desiccator, the 773.9 g. of crude solids are placed in threeliters of benzene and refluxed to remove further water. The benzenemixture is cooled to 40 C. and filtered, and the benzene is distilledofI under 50 mm. Hg to recover 1,1,2, 3,3-pentamethylindanesulfonicacid.

(b) Preparation of pentamethylindanol One mole of the indanesulfonicacid so produced is thoroughly admixed with two moles of sodiumhydroxide, and the mixture is heated to the fusion temperature of 360 C.and maintained at that temperature for two hours. During the fusion thereaction mass is mechanically agitated.

After the heating is completed, the reaction mass is cooled andextracted with water. The product is then neutralized with dilutehydrochloric acid, and the indanol so produced is extracted withbenzene. The benzene is stripped to provide1,1,2,3,3-pentamethylindanol.

(c) Production of pentamethylhexahydroindanol Into a 200 ml. stainlesssteel autocave are introduced 70 g. of 1,1,2,3,3-pentamethylindan-5-ol,5 g. of 5% rhodium on carbon catalyst, and 150 ml. of isopropyl alcohol.While maintaining the temperature within the autoclave at 20 C.,hydrogen gas is fed in until a pressure of 1025 p.s.i. is reached. Whilethe hydrogen pressure is maintained at about 1025 p.s.i., thetemperature of the reaction mass is raised over a period of three hoursto 178 C. (at which point the pressure rises to 1500 p.s.i.).

After eighteen hours of hydrogenation at 1500 p.s.i. and 178 C., thecrude reaction mass is stripped free of solvent. Infrared and NMRanalysis indicate that the reaction mass contains1,1,2,3,3-pentamethylindan-5-ol having the structure Similar reactionsare run with a Raney nickel catalyst at 1500 p.s.i.g. and 200 C. andwith a palladium on carbon catalyst at 150 p.s.i.g. and 200 C. toprovide substantially identical results.

A substantially identical reaction is carried out with1,1,2,3,3-pentamethylindan-4-ol to produce 1,1,2,3,3-hexahydroindan-4-ol having the formula 6 EXAMPLE 11 A 500 ml. reaction flaskis charged with 50 g. of crude hexahydropentamethylindan-S-ol obtainedby hydrogenating the indan-S-ol produced in Example 1. Jones reagent isproduced by dissolving chromium trioxide in 20% aqueous sulfuric acid.The flask contents are maintained at 1520 C. while 75 ml. (0.33 mole) ofthe Jones reagent is added. The reaction flask contents are then stirredfor one-half hour beyond the thirty minutes required for addition of theJones reagent.

The ketone is recovered by adding 25 cc. of methanol and 50 cc. oftoluene. The organic layer is separated, and the remaining aqueous layeris extracted with toluene. The toluene extract is added to the originalextract, and the organic material is washed to neutrality With Water andthen stripped and distilled.

The 33 g. of distilled material is admixed with 2 g. of Primol mineraloil and antioxidant and distilled at a vapor temperature of 96l20 C. at1-2 mm. Hg to obtain 23.5 g. of the pentamethylhexahydro-S-indanone.

The purified material is a clear liquid boiling at 96- 99 C. at 2.0 mm.Hg. The IR spectrum shows significant peaks as follows: at 5.8 microns,at 7.1 microns, and at 7.2 and 7.3 microns. These peaks are attributableto a cyclohexanyl ketone, a methylene adjacent to a carbonyl, and togem-dimethyl and methyl respectively. Raman spectrometry does not showthe presence of any carbonto-carbon unsaturation.

The ketone so obtained has an unmistakeable woody amber odor with a muskquality. This material is compared with a ketone called Ketone BD9, a3,5,5,7,7- pentamethyldecahydro-Z-naphthalenone, and it is found thatthe indanone is a product having a much better woody amber character,whereas said naphthalenone has a simple woody aroma. The fragrancecharacteristics are considered to be quite different.

The process set forth in Example II can be carried out with thecorresponding pentamethylhexahydroindan-4-ol to obtain a fragranceproduct similar to that obtained in Example II.

EXAMPLE III Preparation of 1,1,2,3,3-pentamethylhexahydroindan-4-ol Thefollowing ingredients are charged into a stainless steel five-literautoclave equipped with a hydrogen gas feed:

1,800 g. (8.14 moles) of 1,1,2,3,3-pentamethylindane pure) g. of Raneynickel.

Enough hydrogen is fed into the autoclave to raise the pressure to 1000p.s.i.g. The hydrogen feed is then continued at 3 ml./min., and theautoclave is heated up to a temperature in the range of -185 C. over aperiod of 8 hours. During this time the pressure in the autoclave ismaintained at 1500 p.s.i.g.

The 1641 g. of crude product removed from the autoclave is distilled ona 12-inch Goodloe column after being mixed with 10.0 g. of Primolmineral oil. The distillate is recovered in two fractions:

Fraction I.Distills at a temperature of 7882 C. and 4.0 mm. Hg toprovide 401 g. of 4,5,6,7-tetrahydro- 1,l,2,3,3-pentamethylindane.

Fraction II.Distills at a temperature of 86-88 C. and 3.53.8 mm. Hg toprovide 729 g. of hexahydrol,1,2,3,3-pentamethylindane.

A sample of Fraction I is further refined on a six-foot by inch gasliquid chromatographic (GLC) column containing 20% Carbowax polyethyleneglycol and op- 7 erated at 110 C. Analysis by infrared (IR) and protonmagnetic resonance (PMR) confirms the structure:

Into a 250 ml. flask equipped with thermometer, stirrer, refluxcondenser and ice bath are introduced 195 g. of the tetrahydroindaneproduced above and 15 g. of sodium acetate. At 25 C. to 30 C. 124 g. of40% peracetic acid (0.65 mole) is added during four hours. Afteraddition is completed an equal volume of water is added to the reactionmass. The aqueous phase is separated from the organic phase andextracted with 150 ml. of toluene. The toluene extract is combined withthe organic phase and Washed with one volume of aqueous sodium hydroxidesolution and then with one volume of water.

The solvent is stripped off leaving a crude product weighing 208 g. Thecrude epoxy product is distilled on a 12-inch Goodloe column afteraddition of 4.0 g. of triethanolamine at 7274 C. and 1.0-1.4 mm. Hg.

Into a 5 00 m1. flask equipped with reflux condenser, stirrer,thermometer and addition funnel are introduced 250 cc. toluene and 80 g.aluminum triisopropoxide. The mixture is heated to reflux and 90 g. ofthe epoxyhexahydroindane as produced above is added drop-wise over 1%hours at reflux. The reaction mass is further refluxed for hourswhereupon it is cooled to 25 C.

The cooled reaction mass is poured into a mixture of 500 g. ice and 200cc. of sulfuric acid, stirred for 15 minutes, and separated into anaqueous phase and an organic phase. The aqueous phase is extracted with200 cc. toluene, and the toluene extract is combined with the organiclayer. The bulked material is washed with saturated aqueous sodiumbicarbonate and twice with 100 cc. of water. The solvent is strippedfrom the washed organic phase to provide a crude product weighing 71 g.

The crude product is distilled on a 4-inch microNigreux column at avapor temperature of 105107 C. and 2.1- 2.3 mm. Hg to obtain4,5,6,7-tetrahydro-1,1,2,3,3-pentamethyl-4-indanol.

Into a 200 m1. stainless steel autoclave are introduced 60 g. of theterahydropentamethyl-4-indanol so produced 5 g. of 5% rhodium on carboncatalyst, and 150 ml. of isopropanol. The temperature of the autoclaveis maintained at C. while hydrogen gas is fed in to obtain a pressure of1025 p.s.i.g. The temperature is then raised to 180 C. whereupon thetemperature rises to 1500 p.s.1.g.

After 18 hours of hydrogenation under these conditions, the hydrogen isvented and the autoclave is cooled to room temperature. The solvent isstripped off to yield a crude product weighing 35 g. The product isWashed and distilled to obtain 1,l,2,3,S-pentamethylhexahydrindan-4- ol.

EXAMPLE IV Preparation of 1,1,2,3,3-pentamethylhexahydro-4 (SI-I-indanone Into a 500 ml. flask fitted with cooling means, stirrer,thermometer and reflux condenser are introduced 50 g. of thehexahydroindan-4-ol produced in Example III and 300 ml. of acetone. Themixture is stirred while 75 ml. of Jones reagent is added. The reactionmixture is then stirred for one hour, after which ml. of ethanol and 50ml. of toluene are added. The aqueous phase is removed and the organicphase is washed and neutralized with sodium bicarbonate.

The solvent is stripped off and the remaining organic material isdistilled to provide 1,l,2,3,3-pentamethylhexahydro-4(5H)-indanonehaving a woody amber odor with a fruit-like musk quality.

EXAMPLE V Preparation of soap compositions A total of g. of soap chipsis mixed with one g. of the perfume composition given below until asubstantially homogeneous composition is obtained. The soap compositionmanifests a characteristic woody amber, musk-like odor.

The perfume composition consists of the following ingredients.

Similar results are obtained when the ketone of Example IV is used toreplace the ketone of Example II.

EXAMPLE VI Preparation of a detergent composition A total of 100 g. of adetergent powder is mixed with 0.15 g. of the perfume composition setforth in Example V until a substantially homogeneous composition havinga woody amber or amber-musk like odor is obtained.

EXAMPLE VII Preparation of a cosmetic powder composition A cosmeticpowder is prepared by mixing 100 g. of talcum powder with 0.25 g. of theketone obtained from the process of Example II in a ball mill. A secondcosmetic powder is similarly prepared except that the ketone prepared byExample II is replaced by the compound prepared by Example IV. All havewoody amber, musklike odors.

EXAMPLE VIII Liquid detergent containing1,l,2,3,3pentamethylhexahydroindanones Concentrated liquid detergentswith a woody amber, musk-like odor are prepared containing 0.1%, 0.15%and 0.20% of the ketone produced in Example IV. They are prepared byadding and homogeneously mixing the appropriate quantity of the compoundto P-87 liquid detergent produced by Ultra Chemical Co.

What is claimed is:

1. A saturated indane compound having the formula &

wherein the OH group is in the 4 or the 5 position.

9 10 2. 1,1,2,3,3-pentamethylhexahydro-4-indanol. 2,760,992 8/1956Schoeffel et a1. 260628 3. 1,1,2,3,3-pentarnethy1 hexahydro-S-indanol.3,598,745 8/ 1971 Dunkel 260-617 F References Cited LEON ZITVER, PrimaryExaminer UNITED STATES PATENTS 5 J. E. EVANS, Assistant Examiner2,537,963 1/1951 Cerveny 260631 H 3,193,584 7/1965 Rylander et a1.260-631 H CL 2,754,285 7/1956 Petropoulos 260-628 260-3485 L, 505 C,628, 667

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION IFF 2100A PatentNo, Dated October 23,

ERNST T THEIMER Inventor(s) It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Col. 1, lines 48-55, correct the formula to appear:

Col. 5, line 15, "he" should read the Col. 5, line 43, "autocave" shouldread --autoclave-- Signed and sealed this loth day of April 19%.

(SEAL) Attest:

EDWARD MELETCHERJR C. MARSHALL DANN Attesting Officer Commissioner ofPatents 1 PC3-1050 (IO-69) USCOMM-DC 603756 69 9 U 5 GOVERNMENTPIIINYING OFFICE 19.9 U -'!66-\SA

